Triethylamine → 2,2-Dimethyl-3-(1',1',2',2'-tetrachloroethylthio)-1,3-benzoxazin-4-one

HRID 259226

Reaktionsgleichung

Reaktionsgleichung von HRID 259226
[CH3:1][C:2]1([CH3:13])[NH:7][C:6](=[O:8])[C:5]2[CH:9]=[CH:10][CH:11]=[CH:12][C:4]=2[O:3]1.[Cl:14][C:15]([Cl:21])([S:19]Cl)[CH:16]([Cl:18])[Cl:17].C(N(CC)CC)C>ClCCl>[CH3:1][C:2]1([CH3:13])[N:7]([S:19][C:15]([Cl:21])([Cl:14])[CH:16]([Cl:18])[Cl:17])[C:6](=[O:8])[C:5]2[CH:9]=[CH:10][CH:11]=[CH:12][C:4]=2[O:3]1

Komponenten

5

Edukt 3

HCID 8471TriethylamineHCID 144531,1,2,2-Tetrachloroethylsulfenyl chlorideHCID 7174282,2-dimethyl-3,4-dihydro-2H-1,3-benzoxazin-4-one

Produkt 1

HCID 214236532,2-Dimethyl-3-(1',1',2',2'-tetrachloroethylthio)-1,3-benzoxazin-4-oneAusbeute 15,9 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A 250-ml flask equipped with condenser, stirrer and thermometer and immersed in an ice bath was charged with 150 ml of dichloromethane, 8.3 g (0.047 mol) of 2,2-dimethyl-1,3-benzoxazin-4-one and 10.9 g (0.047 mol) of 1,1,2,2-tetrachloroethylsulfenyl chloride. Then 4.75 g (0.047 mol) of triethylamine dissolved in 10 ml of dichloromethane was added dropwise over a period of 15 minutes. The resulting solution was stirred at 0° C. for 45 more minutes. The crude reaction mixture was washed three times with equal quantities of water. The organic phase was dried and then stripped of solvent. The resulting residue was washed with 200 ml of hexane and filtered. The dried filter cake, 5.1 g, was unreacted 2,2-dimethyl-1,3-benzoxazin-4-one. The filtrate was stripped of hexane and the resulting residue was chromatographed through 300 g of silica gel using 1 liter of hexane, 1 liter of 3% ether-hexane and 3 liters of 5% ether-hexane to give 2.8 g of 2,2-dimethyl-3-(1',1',2',2'-tetrachloroethylthio)-1,3-benzoxazin-4-one. Analysis, calculated for C12H11Cl4NO2S: %C, 37.81; %S, 8.55. Found: %Cl, 40.0; %S, 8.8. NMR spectra confirmed the assigned structure. The infrared spectra had strong adsorption at 1785, 1600, 1460, 1300, 1240 and 740 cm-1. These spectra also had many distinct, medium-strength adsorption bands in the 800-1700 cm-1 region.

Aufarbeitung

  1. customA 250-ml flask equipped with condenser, stirrer
  2. customthermometer and immersed in an ice bath
  3. additionwas added dropwise over a period of 15 minutes
  4. customThe crude reaction mixture
  5. washwas washed three times with equal quantities of water
  6. customThe organic phase was dried
  7. washThe resulting residue was washed with 200 ml of hexane
  8. filtrationfiltered
  9. filtrationThe dried filter cake, 5.1 g
  10. customthe resulting residue was chromatographed through 300 g of silica gel using 1 liter of hexane, 1 liter of 3% ether-hexane and 3 liters of 5% ether-hexane

Quellen und Nachweise

ORD-Eintrag
ord-444e340b7a9046a7a89cad71136e45b3
Quelldatensatz
uspto-grants-1977_07
Patentnummer
US04036960

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